Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
  • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
  • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area

Definitions

• the present invention relates to anti-corrosion pigments based on intercalation compounds, processes for their production and their use.
• Active corrosion protection pigments of great practical importance are red lead, zinc potassium chromate, zinc dust and zinc phosphate.
• Zinc dust coatings with their required high zinc metal contents pose considerable processing problems.
• the zinc phosphate pigments hitherto recommended as corrosion protection pigments have corrosion protection values which are significantly below the values of zinc potassium chromate pigments previously used.
• organic corrosion inhibitors such as have been preferred in aqueous systems, such as For example, use in water cycles has so far often failed.
• solubility ratio in the lacquer especially if it was the salts of the inhibitors.
• the object of the present invention is to develop new active corrosion protection pigments which are at least on a par with the known corrosion protection pigments with regard to their corrosion protection effect and do not have the disadvantages of the known corrosion protection pigments.
• they have a BET specific surface area between 0.1 and 200, preferably between 1 and 150 m 3 / g, and a water-soluble content of less than 0.6, preferably less than 0.3% .
• the divalent metals can be one or more of the group magnesium, calcium, strontium, barium, zinc, iron and manganese, the trivalent metals one or be several of the group aluminum, iron, manganese and chrome.
• the combination of the trivalent aluminum with the likewise colorless alkaline earth metals and / or the zinc cation is particularly preferred, since with suitable organic substances and also inorganic anions, pigments without color strength are obtained which can be colored as desired.
• the group of anhydrides of inorganic acids is formed from the oxides of boron, chromium, carbon, molybdenum, phosphorus and tungsten; carbon dioxide and phosphorus pentoxide are preferred. They can be used individually or in combination.
• the organic substances in the formula mentioned are one or more organic corrosion inhibitors belonging to the prior art and having a Lewis base character.
• the class of effective and storable corrosion inhibitors therefore includes higher amines, aldehydes, Alcohols or ketones, amidines, guanidines, heterocyclic compounds with nitrogen and / or oxygen and / or sulfur as heteroatoms (urotropin, pyrazoles, imidazoles, imidazolines, oxazoles, isoxazoles, thiazoles, isothiazoles, triazoles, triazines, pyridines and the corresponding benzene-fused Systems such as benzimidazoles, benzothiazoles, benzotriazoles, quinolines or isoquinolines, quinazolines and others), sulfur-nitrogen compounds, organic acetylene derivatives, organic nitro compounds and lignin derivatives (sulfonates).
• Phosphonic acids and phosphonocarboxylic acids and their derivatives and salts nitrogen-containing phosphonic or phosphonocarboxylic acids and their derivatives and salts, organic and inorganic salts of carboxylic acids such as acetates, benzoates, cinnamates, salicylates, derivatives and salts of dicarboxylic acids and polycarboxylic acids and polyacrylates, and derivatives of Tannic acids such as tannin and gallic acid and synthetic aromatic oxicarboxylic acids with phenolic character as well as polymers of the polyesters of oxicarboxylic acids with phenolic character.
• suitable mixtures of these agents can also be used.
• these organic reagents which are commonly known as highly hydrophilic, in the binder can surprisingly be reduced so much that corrosion protection pigments which can be processed excellently are produced.
• these do not tend to be for easily soluble pigments or pigments with excessive salt content, typical blistering of the binder under weathering conditions.
• the corrosion protection pigments according to the invention have a proportion of water of crystallization, the exact analytical determination of which is associated with difficulties, since water molecules which are bound more loosely are sometimes present. This can lead to signs of dehydration even at 60 ° C.
• This relatively "volatile" water content strongly depends on the formulation conditions (drying temperature and duration) as well as the crystallinity and particle size of the finished corrosion protection pigment.
• thermogravimetric analysis of the compounds shows that the dehydration of the substances takes place in the relatively large range from 60 to 240 ° C, while the dehydroxylation at temperatures of greater than 160 ° C for Me 2f -rich (here there can be smooth transitions between dehydration and Dehydroxylation), for substances with x values from 0.2 to 0.6 but only occurs above 280 ° C. If one goes over to the Me3 + - rich pigments, a second dehydroxylation step is added at temperatures above 400 ° C.
• the present invention also relates to processes for the preparation of the anti-corrosion pigments of the general formula
• Another method is that basic salts of the di- and / or trivalent metals with the acid form of the inorganic and optionally organic ions at temperatures up to 100 ° C, preferably between 50 and 100 ° C, treated in air and optionally after a previous alkalization in the autoclave at temperatures up to 220 ° C for up to 12 hours.
• Combinations of the two production processes can of course also be carried out, salts of inorganic and organic ions also being able to be used.
• the alkali metering is to be carried out so that the pH of the corrosion protection pigments according to the invention is greater than 6, preferably 7.0 to 8.5.
• the starting compounds in the production of the corrosion protection pigments according to the invention can be their hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, formates, acetates, oxalates and other organic compounds and their active oxides for the divalent metals.
• the metals Zn, Mg, Mn and Fe can also be used as sulfate, Zn also as alkali zincate.
• the trivalent metals can be used as oxide hydroxides, hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, sulfates, formates, acetates, oxalates or organic carboxylates.
• sulfates should be avoided, since otherwise poorly soluble alkaline earth metal sulfates are formed.
• Alkaline substances preferably sodium hydroxide solution, soda, ammonia, ammonium carbonate or mixtures thereof, can be used as precipitants.
• a pH is of greater than 6.0, preferably from 7 to 9, the final pH depending on the metal ions used can be varied and the processed anti-corrosion pigment has a DIN pH of greater than 6, preferably 7 to 8.5.
• Precipitation with an excess of alkalis is advantageous. This leads to excellent crystalline anti-corrosion pigments.
• the heavy elements of group IIa (Ca, Sr and Ba)
• the use is limited to a few percent, since otherwise the binders can be easily saponified and ultimately destroyed as a result of too high basicity.
• the share of. These metals are therefore chosen so that the pH value of the corrosion protection pigment obtained is not above pH 12, preferably not above pH 10. With increasing basicity of calcium via strontium and barium, the content of these alkaline earth metals in the inorganic matrix must be reduced.
• the pH value of the anti-corrosion pigments is determined in accordance with DIN 53 200, the pH value of a suspension of the pigment produced in a fixed manner being measured.
• the corrosion protection pigments according to the invention have specific surfaces according to BET (G. Brunnauer, PH Emmet and H. Teller, H. Amer. Chem. Soc. 60, 309 (1938)) between 0.1 and 200, preferably between 1.0 and 150 m 2 / g.
• the water-soluble proportions are specified in accordance with DIN 53 197.
• the corrosion protection test of the pigments according to the invention was carried out in a salt spray test in accordance with SS DIN 50 021 (Continuous spray with 5% saline at 35 + 2 ° C). Phosphated steel sheets (phosphating process: Bonder 101 from Metallgesellschaft Frankfurt) and degreased bare steel sheets served as the coating medium. The primer was applied by spraying. The following standard test recipe was used:
• the results of the corrosion protection test of the test and comparative pigments are summarized in Table 1.
• the pigments were evaluated according to the following scheme: During the test period, regular samples were taken, in which the sheets were graded from 0 (no damage) to 12 (complete destruction of the paint). The sum of the individual samples of each sheet gives the degree of corrosion, which therefore has a greater value the poorer the corrosion protection capacity of the paint.
• the corrosion protection pigments according to the invention have a corrosion protection effect which is significantly higher than that of the divalent and trivalent metal salts otherwise used. In addition, despite their low slow release properties, they do not show the blistering in the coating which is feared for typically soluble pigments.
• Example 3 The procedure is as in Example 3. Instead of 29.2 g of polycarboxylic acid (Belgard EV, commercial product from Ciba-Geigy) are added to the phosphonopropionic acid.
• Polycarboxylic acid Belgard EV, commercial product from Ciba-Geigy
• the still strongly acidic suspension (pH 5.3) was adjusted to a pH of 8.5 with 166.7 ml of a 2.0 molar Na 1.56 Al (OH) 4.56 solution, and yet another Stirred at 80 ° C for hours, filtered, washed and dried at 105 ° C.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (2)

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• 1981
  • 1981-07-21 DE DE19813128716 patent/DE3128716A1/de not_active Withdrawn
• 1982
  • 1982-07-06 NO NO822359A patent/NO822359L/no unknown
  • 1982-07-07 DE DE8282106055T patent/DE3260897D1/de not_active Expired
  • 1982-07-07 EP EP82106055A patent/EP0070455B1/fr not_active Expired
  • 1982-07-14 US US06/398,226 patent/US4492600A/en not_active Expired - Fee Related
  • 1982-07-19 CA CA000407535A patent/CA1191021A/fr not_active Expired
  • 1982-07-19 JP JP57124539A patent/JPS5825362A/ja active Pending

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